CN109777409B - Long-afterglow near-infrared carbon-based fluorescent nano material and preparation method and application thereof - Google Patents
Long-afterglow near-infrared carbon-based fluorescent nano material and preparation method and application thereof Download PDFInfo
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- CN109777409B CN109777409B CN201910187891.9A CN201910187891A CN109777409B CN 109777409 B CN109777409 B CN 109777409B CN 201910187891 A CN201910187891 A CN 201910187891A CN 109777409 B CN109777409 B CN 109777409B
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Abstract
The invention discloses a long afterglow near infrared carbon-based fluorescent nano material and a preparation and application thereof, comprising the following steps: according to the mass volume ratio of 0.15 g: 0.2 g: respectively weighing 8 mL of zinc gluconate and o-phenylenediamine, dissolving the zinc gluconate and the o-phenylenediamine in water, performing ultrasonic treatment at room temperature to form a uniform mixed solution, then adjusting the pH to 3 by using hydrochloric acid, then filling the mixed solution into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 16.0 hours at 180 ℃, naturally cooling to room temperature to obtain a deep blue liquid, and performing centrifugal separation to obtain a deep blue supernatant, namely the fluorescent nano material with excellent optical performance. According to the invention, a simple hydrothermal synthesis method is adopted to treat a zinc-containing organic matter at a high temperature, and a carbon-based nano material with excellent optical performance is successfully synthesized, and due to the synergistic effect between the doping of metal zinc and o-diamine, the traditional blue light emission of the carbon-based nano material is red-shifted to red light emission, so that the optical performance of the carbon-based nano material is greatly changed. The nano probe material has very good specificity effect on drug micromolecules such as adriamycin and the like, and can realize high-sensitivity detection of the drug micromolecules.
Description
Technical Field
The invention belongs to the field of optics, and particularly relates to a long-afterglow near-infrared carbon-based fluorescent nano material, and a preparation method and application thereof.
Background
Doxorubicin (DOX) is an antitumor antibiotic drug, can inhibit the synthesis of RNA and DNA, has effects on various tumors, belongs to cycle nonspecific drugs, and has killing effects on tumor cells in various growth cycles. Is mainly suitable for acute leukemia, is effective for acute lymphocytic leukemia and granulocytic leukemia, and can be used as a second-line drug, namely, the drug can be considered to be applied when drug resistance is first selected. The major toxic response during administration is a reduction in leukocytes and platelets in about 60% -80% of patients; the hair loss of 100 percent of patients is different; in addition, urine may appear red after administration. Therefore, the method has important biological significance for monitoring the concentration of the adriamycin medicine of a patient taking the medicine in real time. Based on the development prospects of human beings and an ecological system, it is very important to develop a method with high selectivity, high sensitivity, simplicity and effectiveness to monitor the content of the adriamycin in real time. The carbon-based (PLINC) nano material is used as a member of a fluorescent nano material family, and is widely applied to the fields of cell marking, in-vivo imaging, medical diagnosis, environmental analysis and detection and the like due to the excellent optical performance and morphological characteristics of the carbon-based (PLINC) nano material, the occurrence of the carbon-based (PLINC) nano material is expected to initiate a revolution in the field of modern material science, and the application prospect is very wide. The unique optical characteristics and structural composition of the PLINC fluorescent nano material are utilized to be combined with the specificity of the adriamycin drug molecules in blood, so that a sensing device for detecting the low-concentration drug molecules is expected to be prepared. At present, the preparation of water-phase infrared and near-infrared carbon-based fluorescent nano materials is deficient, and the obtained product has low quantum yield and poor selectivity, so that the selectivity and sensitivity of the detection of drug molecules in a complex system are seriously influenced.
Disclosure of Invention
Aiming at the defects of the prior problem, the first object of the invention is to provide a long afterglow near infrared carbon-based fluorescent nano material; the second purpose of the invention is to provide a preparation method of the long afterglow near infrared carbon-based fluorescent nano material; the third purpose of the invention is to provide the application of the long afterglow near infrared carbon-based fluorescent nano material.
According to the invention, a simple hydrothermal synthesis method is adopted to treat zinc-containing organic matters at high temperature, and a PLINC fluorescent nano material with excellent optical performance is successfully synthesized, and due to the synergistic effect between the doping of metal zinc and o-diamine, the traditional blue light emission of the carbon-based nano material is red-shifted to red light emission, so that the optical performance of the carbon-based nano material is greatly changed. Experimental results show that the PLINC nano probe material has very good specific effect on drug micromolecules such as adriamycin and the like, and can realize high-sensitivity detection of the drug micromolecules. The product prepared by the invention can realize high-sensitivity detection of small drug molecules, and can be used in the fields of other optical probes, drug release, preparation of composite carbon-based nano materials and the like due to the unique optical characteristics. The method has simple preparation process and mild operation condition.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a long afterglow near infrared carbon-based fluorescent nano material comprises the following steps: according to the mass volume ratio of 0.15 g: 0.2 g: respectively weighing 8 mL of zinc gluconate and o-phenylenediamine, dissolving the zinc gluconate and the o-phenylenediamine in water, performing ultrasonic treatment at room temperature to form a uniform mixed solution, then adjusting the pH to 3 by using hydrochloric acid, then filling the mixed solution into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 16.0 h at 180 ℃, naturally cooling to room temperature to obtain dark blue liquid, performing centrifugal cleaning, and storing supernatant at 4 ℃ to obtain the fluorescent nano material with excellent optical performance.
As a preferred technical scheme of the application, the ultrasonic time is 1 h.
As a preferred technical scheme of the application, the concentration of the hydrochloric acid is 0.1 mol/L.
As the preferable technical scheme of the application, the centrifugation time is 10 min, and the centrifugation rotating speed is 10000 r/min.
The invention also protects the long-afterglow near-infrared carbon-based fluorescent nano-material prepared by any one of the preparation methods.
The invention also protects the application of the long-afterglow near-infrared carbon-based fluorescent nano material as a fluorescent probe in detecting adriamycin.
As a preferred technical scheme of the application, the method comprises the following specific steps: measuring 10.0 mu L of nanoprobe, placing the nanoprobe in a 2.0 mL centrifuge tube, sequentially adding 10 mu L of Tris-HCl buffer solution and adriamycin standard solutions with different concentrations, and determining the nanoprobe with secondary water after incubationThe volume is 500 mu L, and after standing reaction for 30 min, the change of the maximum fluorescence intensity of the probe is measured under the conditions that the excitation wavelength is 560 nm and the excitation and emission slit widths are both 5 nm; then according to the degree of fluorescence quenching (FL) of the probe618/FL728) Drawing a standard curve; and when the sample to be tested is tested, the corresponding concentration of the sample to be tested is obtained according to the comparison between the fluorescence quenching degree of the sample to be tested and the standard curve.
As a preferred technical scheme of the application, the pH value of the Tris-HCl buffer solution is 6.0, and the concentration is 50 mmol/L.
Advantageous effects
The invention adopts a simple hydrothermal synthesis method to synthesize the uniformly dispersed PLINC fluorescent nano material, effectively expands the emission range of the traditional carbon-based fluorescent material, makes up for the optical properties of the carbon-based fluorescent material in infrared and near infrared, is beneficial to expanding the application range of the carbon-based fluorescent material in medical detection, solves the technical problem of a short plate of the carbon-based material in long-wave emission, and realizes the detection of the small drug molecules with high selectivity and high sensitivity. Fluorescence experiment tests show that the PLINC fluorescent nano material has excellent specificity effect on adriamycin, and high-sensitivity detection of the adriamycin is realized under optimized conditions. The product prepared by the invention can be used for detecting drug molecules, and can also be applied to many fields such as drug delivery carriers, medical research, fluorescent device materials and composite nano materials.
Drawings
FIG. 1 is a diagram of ultraviolet spectrum and emission spectrum under 560 nm excitation of PLINC fluorescent nano material;
FIG. 2 is a plot of excitation wavelength optimization for PLINC fluorescent nanomaterials;
FIG. 3 is the infrared spectrum (FT-IR) of the PLINC fluorescent nanomaterial;
FIG. 4 is a feasibility study of fluorescent detection of doxorubicin by PLINC fluorescent nanomaterial;
FIG. 5 shows fluorescence detection of doxorubicin by PLINC fluorescent nanomaterial;
FIG. 6 is a selective investigation of the PLINC fluorescent nanomaterial.
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instruments used are not indicated by manufacturers, and are regarded as conventional products which can be purchased in the market.
Example 1:
(1) preparing the PLINC fluorescent nano material by a hydrothermal method: weighing 0.15 g of zinc gluconate and 0.2 g of o-phenylenediamine, dissolving in 8 mL of water, performing ultrasonic treatment for 1 h at room temperature to form a uniform mixed solution, then adjusting the pH to 3 with hydrochloric acid (0.1 mol/L), then loading the mixed solution into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 16.0 h at 180 ℃, naturally cooling to room temperature (25 ℃) to obtain a dark blue liquid, performing centrifugal cleaning on the dark blue liquid to obtain the dark blue liquid, performing centrifugal time of 10 min, performing centrifugal rotation at 10000r/min, and storing the centrifugally cleaned dark blue supernatant at 4 ℃ to obtain the PLINC fluorescent nano material with excellent optical performance.
(2) Detection of doxorubicin by PLINC fluorescent nanoprobe: measuring 10.0 mu L of PLINC nanoprobe, placing the PLINC nanoprobe in a centrifuge tube of 2.0 mL, sequentially adding 10 mu L of Tris-HCl buffer solution (pH 6.0, 50 mmol/L) and adriamycin standard solutions with different concentrations, incubating for a few minutes, fixing the volume to 500 mu L with secondary water, and finally standing for reaction for 30 min, and measuring the change of the maximum fluorescence intensity of the PLINC nanoprobe under the conditions that the excitation wavelength is 560 nm and the excitation and emission slit widths are both 5 nm. Then according to the degree of fluorescence quenching (FL) of the PLINC probe618/FL728) And drawing a standard curve.
(3) Sensor selectivity study: respectively extracting a series of 10.0 muL PLINC probe materials, placing the materials in a centrifuge tube of 2.0 mL, sequentially adding 10 muL 50 mmol/L Tris-HCl buffer solution (pH 6.0), and sequentially adding a series of competitive metal cations (including Mg) under the same condition2+，Zn2+，K+And Fe3+) And competitive biological micromolecules (including tyrosine, histidine, glycine, dopamine, adrenalin, ascorbic acid, glucose oxidase and chloramphenicol hydrochloride), incubating for several minutes, diluting with secondary water to 500 μ L, standing for reaction for 30 min, and exciting at excitation wavelength of 560 nmAnd the change of the fluorescence spectrum of the PLINC probe is measured under the test condition that the width of the emitted gap is 5 nm.
The prepared PLINC nanoprobe has an emission wavelength in a near infrared region (618/728 nm, figure 1) through fluorescence spectrum measurement. The optimal excitation wavelength of the PLINC nanoprobe was found to be at 560 nm by optimization of the PLINC nanoprobe excitation wavelength (fig. 2). Meanwhile, FT-IR spectrum analysis shows that the PLINC nano material surface contains a large amount of hydroxyl, carboxyl, amido, amino and other groups (figure 3). In order to verify the feasibility of our experiment, we carried out feasibility analysis on the detection of adriamycin (fig. 4), and the experimental result shows that the PLINC nano material prepared by us has good sensitivity and selectivity on the adriamycin drug molecules. Then, the PLINC nano material with excellent optical performance is used for carrying out high-sensitivity detection on the adriamycin (figure 5), and the result shows that the PLINC nano material has wide linear range and low detection limit on the adriamycin detection. Fig. 6 shows that the sensor constructed by the method is selectively examined under the same conditions (Tris-HCl, pH = 6.0), and the result shows that the PLINC nano-material has good selectivity for detecting doxorubicin, which indicates that the PLINC nano-fluorescent material has good sensitivity and selectivity for doxorubicin.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept and the scope of the appended claims is intended to be protected.
Claims (2)
1. The application of the long afterglow near infrared carbon-based fluorescent nano material as a fluorescent probe in detecting adriamycin is characterized in that: the method comprises the following specific steps: measuring 10.0 muL of nanoprobe, placing the nanoprobe in a 2.0 mL centrifuge tube, sequentially adding 10 muL of Tris-HCl buffer solution and adriamycin standard solution with different concentrations, incubating, diluting the volume to 500 muL with secondary water, and finally standing for reaction for 30 min, and measuring the change of the maximum fluorescence intensity of the nanoprobe under the conditions that the excitation wavelength is 560 nm and the excitation and emission slit width is 5 nm; then according to the fluorescence quenching degree of the probeFL618/FL728Drawing a standard curve; when a sample to be tested is tested, the corresponding concentration of the sample to be tested is obtained according to the comparison between the fluorescence quenching degree of the sample to be tested and the standard curve;
the probe is a long-afterglow near-infrared carbon-based fluorescent nano material and is prepared by the following steps: according to the mass volume ratio of 0.15 g: 0.2 g: respectively weighing 8 mL of zinc gluconate and o-phenylenediamine, dissolving the zinc gluconate and the o-phenylenediamine in water, performing ultrasonic treatment for 1 h at room temperature to form a uniform mixed solution, adjusting the pH to 3 by using 0.1 mol/L hydrochloric acid, then filling the mixed solution into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 16.0 h at 180 ℃, naturally cooling to room temperature to obtain a dark blue liquid, centrifuging for 10 min at the centrifugal rotation speed of 10000r/min, cleaning, and storing supernatant at 4 ℃ to obtain the fluorescent nanomaterial with excellent optical performance.
2. Use according to claim 1, characterized in that: the pH value of the Tris-HCl buffer solution is 6.0, and the concentration is 50 mmol/L.
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| KR101612514B1 (en) * | 2014-06-16 | 2016-04-14 | 포항공과대학교 산학협력단 | Process for preparing carbon quantum dots using emulsion |
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